Process for dimerization,codimerization,polymerization and copolymerization of mono-olefines

ABSTRACT

THE INVENTION RELATES TO A PROCESS FOR THE PREPARATION OF MONO-OLEFINES HAVING A HIGH CONTENT OF B-OLEFINES IN THE RANGE C4-C50 BY DIMERIZATION, CODIMERIZATION, POLYMERIZATION AND COPOLYMERIZATION OF MONO-OLEFINES FROM THE RANGE C2-C15. THE CONVERSION IS PERFORMED IN THE PRESENCE OF A CATALYTIC MIXTURE OF A COMPOUND OF A METAL FROM THE 8TH SUB-GROUP OF THE PERIODIC TABLE, A LEWIS ACID AND, IF DESIRED, A LEWIS BASE AND/OR ELECTRON DONORACCEPTOR COMPOUNDS THEREOF.

United States Patent Oflice Int. c1. 60% 3/10 US. Cl. 260-68315 D 3Claims ABSTRACT OF THE DISCLOSURE The invention relates to a process forthe preparation of mono-olefines having a high content of fl-olefines inthe range C -C by dimerization, codimerization, polymerization andcopolymerization of mono-olefines from the range C -C The conversion isperformed in the presence of a catalytic mixture of a compound of ametal from the 8th sub-group of the periodic table, a Lewis acid and, ifdesired, a Lewis base and/ or electron donoracceptor compounds thereof.

This is a continuation application of copending application Ser. No.630,843, filed Apr. 14, 1967 and now abandoned.

The low-molecular olefines such as ethene, propene, and butene play animportant part as raw materials in large scale industrial organicchemistry.

Among the refining processes for these raw materials the dimerization,codimerization, polymerization and cpolymerization processes withformation of products in the range C -C are of great importance.

From the literature, it is known that beryllium, aluminum, gallium andindium compounds containing Be-H, Al-H, GaH, InH, BeC, AlC, Ga-C or InCbonds are able to add a-olefines forming higher organic beryllium,aluminum, gallium and indium compounds. Reactions of this type areusually called addition reactions (Aufbaureaktionen) according to theoriginal papers by K. Ziegler in this field. Further, it is known thatthe influence of lower a-olefines on higher organic beryllium andaluminum compounds under other reaction conditions may have asubstituting effect, whereby the higher alkyl groups are displaced inthe organometallic compound with the formation of u -olefines. Thisso-called displacement reaction (Verdrangungsreaktion") is catalyzed bymetallic cobalt, platinum and nickel and particularly by metallic nickelin finely divided colloidal form. By a combination of addition reactionwith subsequent displacement reaction, it is thus possible to convertlower a-olefines into higher a-olefines. Thus a dimerization of ethenewith Al(ethyl) as addition catalyst gives n-butene-l, a trimerization ofethene gives nhexene-l, a tetramerization of ethene gives n-octene-l asreaction product, etc. By the dimerization of propene with Al(propyl)/colloidal nickel as catalyst Z-methylpentene-l is formed as reactionproduct (German Pat. No. 964,642, German Auslegeschrift No. 1,178,419and US. Pat. No. 2, 695,327). Drawbacks of the known oligomerizationprocesses of the Ziegler type are, in addition to the heterogenouscharacter of the catalyst systems due to the transition metal addition,that very high catalyst concentrations of the organic beryllium oraluminum compounds are used, up to of the reaction mixture. In additionthese mixtures are highly inflammable and explosive at 3,709,953Patented Jan. 9, 1973 the high temperatures and pressures-up to 250C./200 atm.which are necessary to obtain a satisfactory time yieldduring the syntheses.

*From US. Pat. No. 2,969,408, it is known that additions of nickelcompounds in the form of salts of inorganic and organic acids or in theform of certain organonickel complexes are able to cause the same typeof displacement reaction as colloidal metallic nickel and together withorganometallic halides give a-olefines as primary reaction product. Inthe examples given in the patent the nickel compound is reduced tometallic nickel, which means that the catalyst systems used are of thesame type as the ones discussed above.

Thus, it is a characteristic feature of the known oligomerizationreactions of the Ziegler type that lower a-olefines take part in anaddition reaction and that in the subsequent displacement reactionhigher u-olefines are liberated as reaction product.

Further, it is known from Belgian Pat. No. 651,596 thatwr-allyl-transition metal compounds such as (1r-allyl) Ni or(1r-allyl)Ni-halide in combination with Lewis acid compounds of themetals from the 3rd main group of the periodic table such as Al(C I-I)Cl or AlBr represent active catalyst systems for the oligomerization ofolefines, wherein the catalytic activity is caused by the presence ofthe unstable and easily decomposable transition metal allyl bonds(Angew. Chem., vol. 78, No. 3 (1966) 71). Due to the complicatedcharacter and the partly very unstable nature of the ar-allyl-transitionmetal compounds mentioned above, syntheses and work with such compoundsare bound up with great operational difliculties.

We have now surprisingly found that a series of stable and easilyavailable transition metal compounds of the transition metals from the8th subgroup of the periodic table in combination with Lewis acidcompounds of the elements of the 2nd and 3rd main group represent veryactive, homogeneously acting catalyst systems for dimerization,codimerization, polymerization and copolymerization of mono-olefinesfrom the range C C with the formation of mono-olefines in the range C Chaving a high content of B-olefines, at very low catalyst concentrationsand mild reaction conditions.

Further, we have found that by adding Lewis bases in the form ofcompounds of the elements of the 5th and 6th main group of the periodictable containing one or more of the following functional base groups:

such as ethers, thioethers, disulfides, amines, pyridine compounds,phosphorus trihalides, phosphines, diphosphines, polyphosphines,phosphine oxides, phosphites, arsines and the like, which all inprinciple contain a free electron pair, it is possible to vary theactivity as well as the selectivity of the catalyst systems.

As Lewis acid, use is made of one or more compounds of the type: Al(Y)Ga(Y) In(Y) Be('R) )a-"( )3-aa )a( )3a 0r )a( )3-a, which R represents Hand/or an aliphatic or aromatic hydrocarbon radical containing 1-50carbon atoms, 1s a halide, alcoholate, mercaptide, amine and/orphosphide equivalent, and a is 1 to 2, such as:

The fact that it is also possible to use catalyst systems in whichneither the Lewis acid nor the the transition metal compound (see below)contain metal-carbon bonds is very surprising. A characteristic featureof the prior art catalyst systems for oligomerization of olefines isthat at least one of the catalyst components contains metalcarbon bonds,either in the form of main group metalcarbon bond or in the form oftransition metal-carbon bond. From the literature it appears clearlythat the presence of metal-carbon bonds in at least one of the catalystcomponents is a necessary and vital condition for the catalyticactivity.

As transition metal compound, use is made of one or more compounds ofthe type Me(X) in which Me=transition metal from the 8th subgroup of thepe riodic table, X=an equivalent of an inorganic and/ or organic acidradical, including organic chelate compounds, and n=2 or 3. Illustrativeexamples of such compounds are for instance the following compounds ofcobalt and nickel:

CoCl Ni (CrO CoBr Ni(formate) Co(acetate) Ni(acetate) Co(acetylacetonateh Ni(chloroacetate) Co (propionateh Ni(fluoroacetate) Co(stearateh Ni(benzoate) Co(acetoacetic ester) 3 Ni(stearate) NiCl Ni(oxalate) NiBr Ni(thiophenolate) 2 Nil Ni (oxine) 2 Ni (S Ni(benzoylacetonateJ- Ni(NO Ni(dimethylglyoxime) Ni(SCN) 2 etc.

A characteristic feature of the Me(X) compounds providing the mostadvantageous catalyst systems both with respect to selectivity andactivity, is that they may be coupled directly with said Lewis basecompounds of the elements of the 5th or the 6th main group, or that theymay be coupled indirectly by forming compounds together with the Lewisacid compounds of the elements of the 2nd and 3rd main group which maybe coupled with the above-mentioned types of Lewis bases with theformation of soluble electron donor-acceptor complexes.

The direct or indirect coupling reactions may be performed separately orin situ in the reaction mixture. The direct coupling reactions arepreferably performed separately in polar organic solvents, such asalcohols, ethers and the like, in those cases where Me(X) is slightlysoluble in the reaction medium. The Me(X) -Lewis base compounds areisolated as such and used as catalyst components. Typical Me(X) -Lewisbase compounds which are very active catalyst components are compoundsof the following types:

( )z 2 (II) Me(D--D)X (III) Me(D)X )z a in which D represents a Lewisbase equivalent, D-D is a bifunctional Lewis base attached to Me throughtwo functional base groups, and Me and X are as above. It is alsopossible to use Lewis bases containing more than two Lewis base groupsper molecule.

Examples of compounds of type I:

(tri-ethylphosphine -cobalt-chloride, (pyridine) -cobalt-chloride,

(dioxane -cobalt-chloride,

( tri-n-butylphosphine) -nickel-sulfate, (tri-n-butylphosphine-nickel-chloroacetate, tri-n-butylphosphine -nickel-fiuoroacetate,tricyclohexylpho sphine -nickel-bromide, (tri-iso-propylphosphine)-nickel-iodide, (tri-di-n-butylaminophosphine -nickel-bromide,tri-n-butylphosphine) -nickel-thiophenolate, (tri-n-hexylphosphine-nickel-rhod anide and the like.

Examples of compounds of type II:

( ethylenediamine -nickel-chloride,

(I ,Z-bis-diethylphosphine-ethane )-nickel-bromide,

(2,2'-dipyridyl -nickel-iodid'e,

( 1,5-bis-dicyclohexylphosphino-pentane -nickel-chloroacetate(o-phenanthroline)-nickel-nitrite and the like.

Example of compounds of type III: tri-propylphosphine-nickel-cyclopentadienyl-chloride.

Example of compounds of type IV: (tri-ethylphosphine)-nickel-tribromide.

Example of compounds of type V: (o-phenylene-bis-dimethylarsine)-nickel-trichloride.

Examples of compounds of type VI:

(pyridine -nickel-rhodanide, (pyridine) -cobalt-bromide.

Examples of compounds of type VII:

(ethylenediamine) -nickel-chloride, (ethylenediamine) -cobalt-bromide.

Analogous to the transition metal compounds, the Lewis acid compoundsmay also be coupled with Lewis bases forming Lewis base-Lewis acidcompounds and used in such form in the catalyst system. In the followingexamples of such reactions are given:

By using a Lewis acid-Lewis base compound free Lewis acid and free Lewisbase are simultaneously introduced into the catalyst system since theseare connected to the Lewis acid-Lewis base compounds through equilibriumreactions.

Thus, the Lewis base compounds either may be introduced into thereaction mixture as such or in the form of compounds with transitionmetal compounds and/or Lewis acid compounds.

The formation of the active catalyst system is very simple since thisoccurs at the mixing of the two, possibly three, types of catalystcomponents, preferably in an organic solvent such as chlorobenzene,bromobenzene, chloroform, dichloroethane, methylene chloride, benzene,tolurene, xylene, heptane, higher paraflins and the like in an olefineatmosphere or inert atmosphere.

A characteristic feature of the new catalyst systems described herein isthat Me in the transition metal compound is not substantially reduced tometallic form and that the catalytic activity for the oligomerizationreactions is caused by the presence of soluble transition metalcomplexes. This appears clearly from the selectivity and high activityof the catalyst systems compared with the previously known catalystsystems. Thus the activity of the new catalyst systems is very highalready at as mild conditions as 20 C./l. atm. pressure using Lewisacids such as AlBr and Al(C H )Cl in the catalyst system. In view of theprior art, it is clear that the reactions taking place in the processaccording to the present invention are not an addition reaction and adisplacement reaction of the Ziegler type. That the catalyst systemsused according to the present invention are not previously known also isclear from the composition of the mono-olefines formed, since 5- and'y-olefines are obtained in such high amounts that these cannot havebeen formed entirely by isomerization of a-olefines, but have to beprimary reaction products as well.

Thus, by dimerization of propene to compounds having 2-methylpentenestructure, the fi-olefine 4-methylpentene- 2 is formed as primaryreaction product. In addition, the dimerization of propene under givenreaction conditions may be regulated to give C -olefines having a highcontent of double-branched olefines, such as 2,3-dimethylbutenes.Trimerization of ethene and codimerization of ethene and butene-2 and/or butene-l gives C -olefines having primarily 3-methylpentenestructure, 3-methylpentene-2 being the predominant reaction product.

The selectivity of the catalyst systems is to a great extent dependenton the base strength and the amount of Lewis base used. Thus, catalystsystems containing strong Lewis bases such as tri-n-butylphosphine,tri-cyclohexylphosphine, tri-iso-propyl-phosphine,1,5-bis-dicyclohexylphosphinopentane and tri-n-butylaminophosphine, willgive more products having a higher degree of branching thancorresponding catalyst systems under otherwise similar conditions wheretri-phenylphosphine is used as Lewis base. The amount of branchedreaction products also increases with the amount of Lewis base added.

According to the present invention, it is for instance possible tocodimerize ethene and propene to C -olefines in which more than 90% of C-olefines have iso-pentane structure, by using a strong Lewis base suchas tri-cyclo hexylphosphine in the catalyst system.

In addition to being very active dimerization, codimerization,polydimerization and copolymerization catalysts, the soluble catalystsystems have a partly very rapid double bond isomerizing eifect on theolefines in the reaction mixture. The isomerization activity decreaseswith decreasing reaction temperature, increasing base strength andincreasing amount of the Lewis bases used in the catalyst systems.

By using polar organic solvents in the reaction mixture, higher rates ofreaction are usually obtained than when the reactions are performed in aless polar medium. Thus higher rates of reaction are obtained when usingchlorobenzene or bromobenzene as solvent compared with the otherwisesame system in which benzene or n-heptane is used as solvent. Further,the use of a polar reaction medium will usually favor the formation ofbranched olefines. It is preferred to use a solvent which may easily beseparated from the reaction products when the latter are recovered fromthe reaction mixture.

The concentration of the Lewis acid as well as the molar ratio betweenthe Lewis acid and the transition metal compounds may be varied withinwide limits. For the process the concentration of the Lewis acid issuitably chosen within the range of 0.001-0.100 mole/ liter and themolar ratio of transition metal to Lewis acid in the range 1:10.01:1.

The amount of Lewis base in the catalyst system is suitably chosen sothat the ratio between the base equivalents in the reaction mixture andthe sum of the number of moles of transition metal compounds plus Lewisacid does not exceed 1.6. A ratio in the range 1-0.02 is preferred. Asused herein base equivalent means a Lewis base group having one freeelectron pair. Thus, for example tributylphosphine has one baseequivalent per mole, while 1,5-bis-dicyclohexylphosphinopentane has twobase equivalents per mole.

The present invention provides a process for the preparation ofmono-olefines having a high content of B- olefines from the range C -Cby dimerization, codimerization, polymerization and copolymerization ofmono-olefines. The invention is characterized by the fact that olefinesfrom the range C -C are converted in the presence of catalytic mixturesselected from one or more of the following six types:

Me(X) +Lewis acid+Lewis base Me(X) +Lewis acid-Lewis base Me(X) -Lewisbase+Lewis acid Me(X) -Lewis base+Lewis acid+Lewis base Me(X) -Lewisbase+Lewis acid'Lewis base wherein Me=transition metal from the 8thsubgroup of the periodic table; X-=organic chelate ligand, organicand/or inorganic acid radical; A=Al, Ga and/or In, n=23; Y=halide,alcoholate, mercaptide, amide and/or phosphide equivalent; Lewis acid isAl(Y) Ga(Y) )3, )a( )3-a9 and/0r In(R) (Y) wherein Y has the samemeaning as above, Rzhydrogen and/or aliphatic or aromatic hydrocarbonradical containing l-50 carbon atoms, and a=12; Lewis base is a mono-,dior polyfunctional organic or inorganic compound containing one or moreof the following base groups:-

and Me(X) -Lewis base and Lewis acid-Lewis base represent electrondonor-acceptor compounds of Lewis base with Me(X) and Lewis acidrespectively; at such a low temperature that Me in the compounds Me(X)are not substantially reduced to metallic form, preferably at atemperature not above C.

The process according to the invention may be performed at pressuresfrom fractions of an atmosphere up to very large pressures, limited onlyby the apparatus construction. It is, however, advantageous, out ofregard for temperature control, that the reactions take place atpressures not exceeding 100 atm. If a catalyst combination with pureinorganic Lewis acids such as AlBr is employed, the temperature may bevaried within wide limits, preferably not above C. However, if theprocess is performed with organometallic Lewis acids in the catalystsystem, such as Al(alkyl) (halide), Al(aryl) (halide) Al(alkoxy) (alkyl)(halide), Be(alkyl) Ga(alkyl) (halide) or In(alkyl) (halide) thereducing effect which lies in the main group metal-carbon bonds BeC,AlC, Ga-C and InC may lead to a reduction of the transition metalcompounds if the temperature during the reaction becomes too high. Thereaction temperature should therefore suitably be kept below thetemperature range in which a substantial part of the transition metalcompound during the reaction is reduced to metallic form. Such areduction may be observed as a blackening of the solution due toprecipitation of transition metal. The highest reaction temperature maybe employed in the processes utilizing the most stable transition metalcompounds in combination with the least reduction active organic maingroup metal compounds, but should preferably not exceed 100 C.

The process can be carried out either discontinuously, for example, bycharging the catalyst components together with a solvent, if necessary,into a thermostatregulated reaction vessel, passing the monomer or themonomer mixture into the catalyst mixture for some time, e.g. 1-5 hours,and then recovering the reaction product by the usual working-upmethods, or continuously, for example by passing the monomer or themonomer mixture through the catalyst mixture if desired under pressure,with subsequent continuous isolation of the reaction product from theoutflowing reaction mixture. Unreacted monomer and solvent, if any, andcatalyst are separated from the reaction product during the isolation ofthe latter and are suitably recirculated to the reaction vessel. By theprocess according to the invention, when the monomer is a liquid,solvent can be omitted with advantage.

As starting material for the process, there may be used both aandB-olefines or olefines in which the double bond is situated further intothe molecule.

APPARATUS AND TECHNIQUE For Examples 1-14 and 16-47 the followingapparatus and work technique are used:

One or more of the above-mentioned types of transition metal compoundstogether with possible Lewis'base compound, are charged into athermostat-regulated glass reaction flask, equipped with a magneticstirrer, reflux condenser and dropping funnel with pressure-equalizingmeans. n the top of the reflux condenser there is a possibility ofconnection to vacuum, highly purified argon and starting-monomer for thesyntheses. Under argon flush the desired quantity of abs. solvent(distilled over P 0 and LiAlH or Na and organo-aluminnm compounds) isadded to the reaction vessel. (In those cases where volatile Lewis basesare used, e.g. tri-butyl-phosphine, these are added to the reactionvessel at this stage.) A Lewis acid of the above-mentioned type ormixtures of these are, if necessary diluted with solvent, then added tothe dropping funnel in argon atmosphere. The whole apparatus is thencarefully evacuated three times and after each time filled withstarting-monomer required to maintain constant pressure in the reactionflask (1 atm.) is measured with a capillary flow meter as a function ofreaction time. The bath temperature is kept constant within the limits$0.05 C. by means of a water-circulation thermostat. After a certainreaction time the conversion is stopped and the reaction mixture isgas-chromatographically analyzed.

For examples 15 and 48-54 the following apparatus and work technique areused:

The reaction is carried out in a non-magnetic, acidresistant steelautoclave having a volume of 200 ml. The autoclave is connected with aglass container which could be evacuated. The connection between the twovessels could be closed by means of a high pressure valve. Before therun, the autoclave and glass container are evacuated to less than 0.5mm. Hg in 30 min. The valve between the two vessels is closed and theglass container filled with highly purified nitrogen. The catalystcomponents and the solvent are then poured into the glass container innitrogen atmosphere.

By opening the valve between the two vessels, the catalyst solution issucked into the evacuated autoclave. The connection to the vacuum pumpis cut off in advance. The autoclave is then filled with monomer to theindicated pressure, which is kept constant during the whole reactionperiod. The autoclave is fitted with magnetic stirrer and stood in awater bath with the stated temperatures 20.1 C. The reaction mixturesare gas-chromatographically analyzed.

In the examples, atm. is atmosphere(s), ml. is milliliter(s), mg. ismilligrams, min. is minute(s). Percentages are by weight.

8 EXAMPLE 1 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 25 mg. nickel(II) chloride, 25.3 mg. tri-n-butylphosphine and63.5 mg. aluminum-monoethyl-dichloride.

Reaction time: 30 min.

Reaction product formed: 9 ml.

Composition of product 78.0% C -olefins (of which 2.3% butene-l,

butene-Z-trans and 29.1% butene-Z-cis),

20%.C -olefines (of which 0.9% 3-methylpentene-1, 2.2%

hexene-3-cis/ trans, 17.3% 2-ethylbutene-1, 9.6% hexene-Z-trans, 24.7%3-methylpentene-2-trans and 45.3% 3 -methyl-pentene-2-cis) k EXAMPLE 2Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 22 mg. nickel(II)acetylacetonate, 25.3 mg. trin-butylphosphineand 63.5 mg. aluminum-monoethyldichloride.

Reaction time: 60 min.

Reaction product formed: 22 ml.

Composition of product 47% C -olefines (of which 2.2% butene-l, 71.4%butene- Z-trans and 26.4% butene-Z-cis),

43% C -olefines (of which 0.4% 3-methylpentene-1, 2.7%hexene-3cis/trans, 12.9% 2-ethylbutene-l, 9.4% hexene-Z-trans, 25.0%3-methylpentenea2-trans and 49.6% B-methylpe ntene-Z-cis 10% C -olefinesand higher.

EXAMPLE 3 Composition of product 96% C -olefines (of which 2.9%butene-l, 68.7% butene- 2-trans and 28.4% butene-Z-cis),

1% c -olefines and higher.

EXAMPLE 4 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 16 mg. nickel(II)acetylacetonate, 25.3 mg. trin-butylphosphineand 133 mg. aluminum trihromide.

Reaction time: 30 min.

Reaction product formed: 11 ml.

Composition of product C -olefines (of which 1.2% butene-l, 71.6%butene- 2-trans and 27.2% butene-Z-cis),

13% C -olefines (of which 4.5% 3-methylpentene-l, 9.3% hexene 3cis/trans, 23.8% hexene 2 trans, 14.8% 3-methylpentene-2-trans, 11.5%hexene-Z-cis and 36.1% 3-methylpentene-2-cis),

7% C 01efines and higher.

9 EXAMPLE 5 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 16 mg. nickel(II)acetylacetonate, 38.2 mg. triphenylarsine and63.5 mg. aluminum-monoethyl-dichloride.

Reaction time: 60 min.

Reaction product formed: 12 ml.

Composition of product 72% C -olefines (of which 2.0% butene-l, 70%butene- 2-trans and 28% butene-Z-cis),

26% C -olefines (of which 5.5% hexene-3-cis/ trans, 3.6%2-ethylbutene-1, 14.3% heXene-2-trans, 25.9% 3-rnethylpentene-Z-transand 50.7% 3-methyl-pentene-2-cis),

2% C -olefines and higher.

EXAMPLE 6 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 16 mg. nickel(II)acetylacetonate, 21.2 mg. diphenylether and63.5 mg. aluminum-monoethyl-dichloride.

Reaction time: 30 min.

Reaction product formed: 12 ml.

Composition of product 60% C -lefines (of which 2.5% butene-l, 70%butene- 2-trans and 27.5% butene-Z-cis),

37% C -olefines (of which 0.5% 3-methylpentene-1, 7.6% hexene-3cis/trans, 19.4% heXene-2-trans, 26.9% 3-methyl-pentene-2-trans and45.6% 3-methylpentene-Z-cis) 3% C -olefines and higher.

EXAMPLE 7 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 11 mg. cobalt(II)acetate, 38.2 mg. triphenylphosphine and 63.5mg. aluminum-monoethyl-dichloride.

Reaction time: 30 min.

Reaction product formed: ml.

Composition of product 94% C -0lefines (of which 2.2% butene-1, 69.6%'butene- 2-trans and 28.2% butene-Z-cis),

5% C olefines (of which 7.7% 3-methylpentene-1, 5.8%

hexene-3-cis/trans, 19.2% Z-ethyIbutene-l, 13.5% 3-methyl-pentene-Z-trans, 7.7% heXene-2-cis and 26.9%3-methyl-pentene-2-cis) 1% C -olefines and higher.

EXAMPLE 8 Temperature: 20 C. Pressure: 1 atm. Solvent: 25 m1.chlorobenzene.

Monomer: Ethene/Propene=1/1 (gas volume 20 C.). Catalyst: 11 mg.nickel(II)acetate, 30.6 mg. triphenylamine and 63.5 mg.aluminum-monoethyl-dichloride.

Reaction time: 30 min. Reaction product formed: 19 ml.

Composition of product 9.5% C -olefines (of which 2.6% butene-l, 69.4%butene-2-trans and 28.0% buteue-Z-cis),

51.5% C -olefines (of which 44.2% n-pentene isomers and 55.8%2-methylbutene isomers),

10 33.0% C -olefines (of which 52.9% 2-methylpentene isomers, 9.9%n-hexene isomers, 25.0% 3-methylpentene isomers, 10.2%2,3-dimethylbutene isomers and 2.0% 2-ethylbutene isomers), 6%Cq-OlCfiHGS and higher.

EXAMPLE 9 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 11 mg. nickel(II)acetate, 13.7 mg. diphenyldisulphide and 63.5mg. aluminum-monoethyldichloride.

Reaction time: 30 min.

Reaction product formed: 15 m1.

Composition of product 94% C -olefines (of which 0.4% 4-methylpentene-1,

1.2% 4-methylpentene-2-cis, 9.6% 4-methylpentene-2- trans, 6.3%2-methylpentene-1, 4.8% hexene-3-cis/ trans, 13.2% hexene-Z-trans, 56.6%2-methylpentene 2, 4.1% hexene-2-cis and 3.9% 2,3-dimethylbutene-2),

6% C -olefines and higher.

EXAMPLE 10 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 11 mg. nickel(II)acetate and 133 mg. aluminum-tri-bromide.

Reaction time: 30 min.

Reaction product formed: 5 ml.

Composition of product 95% C -olefines (of which 2.3% 4-methylpentene-1,

8.1% 4-methylpentene-2-cis, 62.1% 4-methylpentene-2- trans, 1.6%Z-methylpentene-l, 4.4% hexene-3-cis/ trans, 18.3% 2-methy1pentene-2 and4.5% hexene-Z- cis),

5% C -olefines and higher.

EXAMPLE 1 1 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. benzene.

Monomer: Propene.

Catalyst: 33.4 mg. di-(tri-n-butylphosphine)-nickel(II) chloride and63.5 mg. aluminum-monoethyl-dichloride.

Reaction time: 30 min.

Reaction product formed: 28 ml.

Composition of product 88% C -0lefines (of which 0.7% 4-methylpentene-1,

2.8% 4-methylpentene-2-cis, 32.2% 4-methylpentene- 2-trans, 8.5%2-methylpentene-1, 2.1% heXene-3-cis/ trans, 6.2% hexene-2-trans, 39.3%2-methylpentene-2, 1.6% heXene-Z-cis and 6.6 2,3-dimethylbutene-2),

12% C -olefines and higher.

1 1 EXAMPLE 13 Composition of product 98.0% C -oiefines (of which 0.5%4-methylpentene-1,

1.8% 4-methylpentene-2-cis, 21.1% 4-rnethylpentene-2- trans, 9.7%2-methylpentene-1, 3.1% hexene-3-cis/ trans, 9.4% hexene-Z-trans, 45.7%Z-methylpentene-Z, 2.8% hexene-2-cis and 5.9% 2,3-dimethylbutene-2),

2% C -olefines and higher.

EXAMPLE 14 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 15.6 mg. NiBr [P(n-butyl) and 253.92 mg.

Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 34 ml.

Composition of product 96.0% C -olefines (of which 0.9%4-methylpentene-1,

3.4% 4-methylpentene-2-cis, 23.5% 4-Inethy1pentene-2- trans, 0.4%2-methylpentene-1, 2.3% hexene-3-cis/ trans, 6.2% hexene-Z-trans, 41.4%2-methylpentene-2, 2.4% hexene-3-cis and 19.5% 2,3-dimethylbutene-2),

4% C -o1efines and higher.

EXAMPLE 15 Temperature: C.

Pressure: 7 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene Catalyst: 11 mg. nickel(II)acetate, 38.2triphenylphosphine and 63.5 mg. Al(ethyl)Cl Reaction time: 15 min.

Reaction product formed: 35 ml.

Composition of product 63% C -o1efines (of which 1.9% butene-l, 71.5%butene- Z-trans and 26.6% butene-2-cis),

32% C -0lefines (of which 4.0% hexene-3-cis/trans, 14.5%2-ethylbutene-l, 15.3% hexene-Z-trans. 22.8% 3-methylpentene-2-trans and43.4% 3-rnethylpentene-2- C18), 5% C -olefines and higher.

EXAMPLE 16 Temperature: 40 C.

Pressure: 1 atm.

Solvent: ml. chlorobenzene.

Monomer: Propene.

Catalyst: 15.6 mg. NiBr [P(n-butyl) and 15.87 mg.

Al(ethy1)Cl Reaction time: min.

Reaction product formed: 13 ml.

Composition of product 93.0% c -olefines (of which 0.8%4-methylpentene-1,

1.7% 4-methylpentene-2cis, 14.6% 2,3-dimethylbutene- 1, 16.1%4-methylpentene-2-trans, 1.4% hexene-l, 6.9% Z-methylpentene-l, 1.6%hexene-3-cis/trans, 4.3% hexene-Z-trans, 38.1% 2-methyIpentene-2, 1.7%hexene-2-cis and 12.8% 2,3-dimethylbutene-2),

7% C olefines and higher.

12 EXAMPLE 17 Temperature: 0 C.

Pressure: 1 atm.

Solvent: 25 ml. n-heptane.

Monomer: Propene.

Catalyst: 17.25 mg. NiBr [P(cyc1ohexyl) and 15.87

mg. Al(ethyl)Cl Reaction time: 60 min.

Reaction product formed: 9 ml.

Composition of product 91.9% C -olefins (of which 5.4%4-methy1pentene-l,

3.2% 4-methylpentene-2-cis, 50.1% 2,3-dimethylbutone-1, 8.0%4-methyipentene-2-trans, 25.0% Z-methylpentene-l, 2.3% hexene-Z-trans,2.3% Z-methyipentene- 2, 2.4% hexene-2-cis and 1.4%2,3-dimethylbutene-2),

8.1% C -olefines and higher.

EXAMPLE 18 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 43.2 mg. Ni(NO [P(phenyl) and 63.48

mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 19 ml.

Composition of product 87.5% c -olefines (of which 0.7%4-methylpentene-l,

1.4% 4-methylpentene-2-cis, 24.0% 4-methy1pentene-2- trans, 9.9%2-methylpentene-1, 4.2% heXcne-3-cis/ trans, 9.3% hexene-Z-trans, 44.3%2-methy1pentene-2, 4.0% hexene-2-cis and 2.1% 2,3-dimethylbutene-2),

12.5% C -olefines and higher.

EXAMPLE 19 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propeue.

Catalyst: 36.3 mg. Ni(SCN) -['P(n-butyl) and 63.48

mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 18 ml.

Composition of product 95.4% c -olefines (of which 0.8%4-methylpentene-1,

1.6% 4-methylpentene-2-cis, 35.7% 4-methylpentene- Z-trans, 7.8%Z-rnethylpentene-i, 1.8% heXene-3-cis/ trans, 4.5% hexene-2-trans, 38.9%2-methylpentene-2, 1.8% heXene-2-cis and 6.9% 2,3-dimethylbutene-2),

4.6% C -olefines and higher.

EXAMPLE 20 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 52.3 mg. NiI -[P(pheny1) and 63.48 mg.

Al(ethy1)Cl Reaction time: 30 min.

Reaction product formed: 19 ml.

Composition of product 94.1% c -olefines (of which 0.4%4-methylpentene-l,

1.2% 4-methylpentene-2-cis, 20.9% 4-methylpentene-2- trans, 8.7%Z-methylpentene-l, 4.2% hexene- 3 -cis/ trans, 8.6% hexene-Z-trans,48.8% Z-methylpentene-Z, 3.5% hexene-Z-cis and 3.8%2,3-dirnethylbutene-2),

5.9% c -olefines and higher.

13 EXAMPLE 21 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 34.9 mg. NiSO -[P(n-butyl) and 63.48 mg.

Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 32 ml.

Composition of product 93.6% C -olefines (of which 0.4%4-methylpentene-1,

1.3% 4-methylpentene-2-cis, 30.1% 4-methylpentene- 2-trans, 6.8%2-methylpentene-1, 0.9% hexene-S-cis/ trans, 2.8% hexene-Z-trans, 42.9%2-methylpentene-2, 2.4% hexene-Z-cis and 12.4% 2,3-dimethylbutene-2),

6.4% C -o1efines and higher.

EXAMPLE 22 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 23.2 mg. NiCl -[2,4,6-trimethylpyridine] and 63.48 mg.Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 34 ml.

Composition of product 84.0% C -olefines (of which 0.7%4-methylpentene-1,

1.9% 4-methylpentene-2-cis, 14.5% 4-methylpentene-2- trans, 1.3% 2methylpentene 1, 4.5% hexene-3-cis/ trans, 12.3% hexene-2-trans, 53.5%2-methylpentene-2, 5.0% hexene-Z-cis and 6.2% 2,3-dimethylbutene-2),

16% C -olefines and higher.

EXAMPLE 23 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 38.5 mg. NiCl -[P(N(ethyl) and 63.48

mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 19 ml.

Composition of product 96.1% C -olefines (of which 0.4%4-methylpentene-1, 1.1% 4-methylpentene-2-cis, 13.6% 2,3-dimethylbutene-1, 17.4% 4-methylpentene-2-trans, 6.7% Z-methylpentene-l, 2.4%hexene-3-cis/trans, 6.1% hexene-Z-trans, 41.2% Z-methylpentene-Z, 2.2%hexene-Z-cis and 8.9% 2,3-dimethylbutene-2),

3.9% C -olefines and higher.

EXAMPLE 24 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 45.1 mg. NiCl -[PO(cyclohexyl) and 63.49

mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 15 m1.

Composition of product 93.3% C -olefines (of which 0.5%4-methylpentene-l,

1.9% 4-methylpentene-2-cis, 11.7% 4-methylpentene-2- trans, 3.8%Z-methyIpentene-l, 5.1% hexene-3-cis/ trans, 13.5% hexene-Z-trans, 53.8% 2-methylpentene-2, 4.9% heXene-Z cis and 4.8% 2,3-dimethylbutene-2),

6.7% C -olefines and higher.

EXAMPLE 25 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 12.1 mg. NiCI -[ethylenediamineh and 63.48

mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 7 ml.

Composition of product 92.5% C -olefines (of which 1.8%4-methylpentene-1,

6.4% 4-methylpentene-2-cis, 46.4% 2,3 -dimethyl'butene-1 plus4-methylpentene-2-trans, 5.6% hexene-3- cis/trans, 14.8% hexene-Z-trans,17.4% 2-methylpentene-2, 4.8% hexene-2-cis and 2.7%2,3-dimethylbutone-2),

7.5% C -olefines and higher.

EXAMPLE 26 Temperature: 10 C. Pressure: 1 atm. Solvent: 25 ml.chlorobenzene. Monomer: Ethene:Butene-2 (1:1 gas volume). Catalyst: 7.26mg. NiCl -[P(isopropyl) 10.0 mg. P-

(isopropyl) and 31.74 mg. Al(ethyl)Cl Reaction time: 30 min. Reactionproduct formed: 22 ml.

Composition of product 71.8% C -olefines (of which 2.9% butene-l, 61.2%butene-Z-trans and 35.9% butene-Z-cis),

20.0% C -olefines (of which 10.5% 3-methylpentene-1,

41.0% Z-ethylbutene-l, 6.8% hexene-Z-trans, 7.8% 3-methylpentene-Z-trans, 3.1% hexene-Z-cis and 31.6%3-methylpentene-2-cis) 8.2% C -olefines and higher.

Composition of product 88.0% C -olefines (of which 13.4% butene-l, 53.9%

butene-Z-trans and 32.7% butene-Z-cis),

9.6% C -olefines (of which 7.9% 3-methylpentene-1,

3.9% hexene-l, 5.9% 2-ethylbutene-1, 17.3% hexene- 2-trans, 2.4%3-methylpentene-2-trans, 6.3% hexene-Z- cis and 6.3%3-methylpentene-2-cis),

2.4% C -olefines and higher.

EXAMPLE 28 Temperature: 10 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 5.03 mg. Ni(chloroacetate) -[P(cyclohexyl) 35.0 mg.P(cyclohexyl) and 31.74 mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 16 ml.

Composition of product 69.7% C -olefines (of which 10.2% butene-l, 53.0%

butene-Z-trans and 36.8% butene-Z-cis),

24.0% C -olefines (of which 8.2% 3-methylpentene-1,

1.4% hexene-l, 60.1% Z-ethyIbutene-l, 8.1% hexene- 2-trans, 4.6%3-methylpentene-2-trans, 5.4% hexene-Z- cis and 12.3% 3-methylpentene-2cis),

6.3% C -olefines and higher.

1 EXAMPLE 29 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 m1. chlorobenzene.

Monomer: Ethene.

Catalyst: 4.37 mg. NiCrO 10.0 mg. P(isopropyl) and 31.64 mg. Al(ethyl)ClReaction time: 30 min.

Reaction product formed: 5 ml.

Composition of product 77.7% C -olefines (of which 7.5% butene-l, 63.3%butene2-trans and 29.2% butene-Z-cis),

18.2% C -olefines (of which 4.1% 3-methylpentene-1,

3.8% hexene-l, 21.4% Z-ethyIbutene-l, 35.3% hexene- Z-trans, 7.3%B-methylpentene-Z-trans, 9.0% hexene-Z- cis and 19.2%methylpentene-Z-cis),

4.1% C -olefines and higher.

EXAMPLE 30 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 m1. dichloroethane.

Monomer: Ethene.

Catalyst: 6.67 mg. NiC1 -[P(n-butyl) 15.87 mg. Al

(ethyl) C1 At reaction times 15 and 30 min. samples for analysis weretaken from the reaction mixture. The samples had the followingcompositions respectively:

Reaction time: 15 min.

Composition of product 72.0% C -olefines (of which 1.6% butene-I, 70.9%

butene-Z-trans and 27.4% butene-Z-cis),

22.8% C -olefines (of which 0.9% 3-methylpentene-1,

9.2% Z-ethylbutene-l, 17.5% hexene-Z-trans, 20.7% 3-methylpentene-2-trans, 5.4% hexene-Z-cis and 46.3% 3-methylpenteue-Z-cis) 5.2% c -olefines and higher Reaction time: 50 min.

Composition of product Composition of product 50.9% C -olefines (ofwhich 2.4% butene-l, 70.3%

butene-Z-traus and 27.3% butene-Z-cis),

42.5% C -olefines (of which 0.9% B-methylpentene-l,

9.9% Z-ethyIbutene-l, 7.9% hexene-Z-trans, 24.6% 3-methylpentene-Z-trans, 4.8% heXene-Z-cis and 51.9% 3-methylpentene-Z-cis),

6.6% C -olefines and higher.

The run was stopped after a reaction time of 60 min.

Reaction product formed: 17 ml.

EXAMPLE 31 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 17.3 mg. NiBr(NO) [P(phenyl) and 31.74

mg. l(ethyl)Cl Reaction time: 30 min.

Reaction product formed: ml.

Composition of product 79.7% C -olefines (of which 2.3% butene-1, 68.7%

butene-Z-trans and 29.0% butene-Z-cis),

18.8% C -olefines (of which 1.0% 3-methylpentene-1, 12.6%2-ethylhutene-1, 12.3% hexene-2-trans, 24.4% 3-methylpentene-2-trans,9.0% heXene-Z-cis and 40.7% 3-methylpentene-2-cis) 1.5% C -olefines andhigher.

EXAMPLE 32 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 13.9 mg. Ni(NO -[P(n-butyl) and 31.74

mg. Al(ethy1) Cl Reaction time: 30 min.

Reaction product formed: 15 ml.

Composition of product 40.2% C -olefines (of which 3.0% butene-l, 67.3%butene-Z-trans and 29.7% butene-Z-cis),

55.4% C -olefines (of which 0.3% 3-methylpentene-1,

7.3% Z-ethylbutene-l, 4.3% heXene-Z-trans, 29.1% 3-methylpentene-2-trans, 1.5% hexene-Z-cis and 57.5%3-methylpentene-2-cis) 4.4% c -olefines and higher.

EXAMPLE 33 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 6.67 mg. NiCl -[P(n-buty1) and 15.1 mg.

Al(ethy1) Cl.

Reaction time: 15 min.

At reaction time 15 min., a sample was taken fromthe reaction mixturefor analysis. It had the following composition:

Composition of product 81.4% C -olefines (of which 2.5% butene-1, 70.1%hutene-Z-trans and 27.4% butene-Z-cis),

17.0% C -olefines (of which 20.5% 2-ethylbutene-1, 12.0% hexene-Z-trans,21.7% 3-methylpentene-2-trans, 6.0% hexene-Z-cis and 39.8%3-methylpentene-2-cis),

1.6% C olefines and higher.

Reaction time: 60 min.

Composition of product 75.8% C -olefines (of which 2.2% butene-l, 70.9%butene-Z-trans and 26.9% butene-Z-cis),

22.6% C -olefines (of which 0.7% 3-methylpentene-1, 20.1%2-ethylbutene-1, 11.0% hexene-Z-trans, 22.0% 3-methylpentene-2-trans3.5% hexene-2-cis and 42.5% 3-methylpentene-2-cis) 1.6% C -olefines andhigher.

The run was stopped after a reaction time of 60 min.

Reaction product formed: 12 ml.

EXAMPLE 34 Temperature: 20 C. Pressure: 1 atm. Solvent: 25 m1. benzene.Monomer: Ethene. Catalyst: 66.7 mg. NiCl [P(n-buty1)3]2, 32.75 mg.

P(pheny1) and 16.8 mg. Be(ethyl) Reaction time: 30 min. Reaction productformed: 8 ml.

Composition of product 89.5% C -olefines (of which 2.4% butene-l, 68.8%butene-Z-trans and 28.8% butene-Z-cis),

8.5% C -olefines (of which 6.7% hexene-3-cis/trans, 22.4%2-ethylbutene-1, 20.2% hexene-Z-trans, 18.0% 3-methylpente11e-2-transand 32.7% 3-methylpentene-2- cis),

2.0% C -olefines and higher.

EXAMPLE 35 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 6.67 mg. NiCl -[P(n-butyl) and 15.5 mg.

Al (ethy1) Cl At reaction time 15 min. a sample was taken from thereaction mixture for analysis. It had the following composition:

Composition of product 57.5% C -olefines (of which 2.0% butene-l, 69.6%butene-Z-trans and 28.5% butene-2-cis),

39.2% C -0lefines (of which 0.3% 3-methylpentene-1,

10.1% 2-ethylbutene-1, 7.2% hexene-2-trans, 26.7% 3-methylpentene-2-trans, 5.3% hexene-2-cis and 50.4%3-methylpentene-2-cis) 3.3% C -olefines and higher.

The run was stopped after a reaction time of 60 min.

Reaction product formed: 17 ml.

Composition of product 53.9% C -0lefir1es (of which 2.2% butene-l, 71.6%butene-2-trans and 26.2% butene-2-cis),

42.1% C -olefines (of which 0.4% 3-methylpentene-1,

12.5% 2-ethylbutene-1, 6.8% heXene-2-trans, 39.3% 3-methylpentene-Z-trans, 4.3% hexene-Z-cis and 36.7% 3-methylpentene-2-cis 4.0% C -olcfines and higher.

EXAMPLE 36 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. benzene.

Monomer: Propene.

Catalyst: 6.1 mg. Ni(Cl-acetate) and 97.5 mg.

Al (ethyl C1 P (phenyl) 3 Reaction time: 30 min. Reaction productformed: m1.

Composition of product 92% C -olefines (of which 0.5% 4-methylpentene-1,2.5% 4-methylpentene-2-cis, 2.0% 2,3-dimethylbutene-1, 26.1%4-methylpentene-2-trans, 3.0% 2-methy1pentene- 1, 3.5% hexene-3-cis/trans, 11.0% heXene-Z-trans, 40.8% 2-methylpentene-2, 2.5 heXene-Z-cisand 8.1% 2,3-dimethylbutene-2) 8% C -olefines and higher.

EXAMPLE 37 Temperature: C.

Pressure: 1 atm.

Solvent: ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 8.2 mg. Ni(SC H [P-( ynalz and 63.48 mg. Al(ethyl)Cl Reactiontime: min.

Reaction product formed: 17 m1.

Composition of product 41.7% C -olefines (of which 2.1% butene-l, 71.7%butene-2-trans and 26.2% butene-2-eis), 47.7% C -olefines (of which 0.3%3-methylpentene-1,

18 2.9% 2-ethylbutene-1, 4.0% hexene-2-trans, 28.8% 3-methylpentene-Z-trans, 64.1% 3-methylpentene-2-cis), 10.6% C -olefinesand higher.

EXAMPLE 38 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 8.53 mg. cobalt(III) acetylacetonate and 62.0

Al (ethyl) Cl Reaction time: 30 min.

Reaction product formed: 2 ml.

Composition of product C -olefines (of which 2.0% butene-l, 69.8%butene- Z-trans and 29.2% butene-Z-cis), 5% C -olefines and higher.

EXAMPLE 39 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 m1. chlorobenzene.

Monomer: Ethene.

Catalyst: 9.77 mg. (C H )Ni- [P(phenyl) ]CH and 63.48 mg. A1(ethyl)ClReaction time: 30 min.

Reaction product formed: 6 ml.

Composition of product 95.9% C -olefines (of which 2.5% butene-l, 69.4%

butene-2-trans and 28.1% butene-Z-cis),

3.3% C -olcfins (of which 6.7% 3-methylpentene-1, 22.5% Z-ethylbutene-l,22.5% hexene-Z-trans, 12.4% 3-methylpentene-2-trans, 11.2% hexene-Z-cisand 24.7% 3-methylpentene-2-cis),

0.8% C -olefincs and higher.

EXAMPLE 40 Composition of product 70.6% C -olefins (of which 2.2%butene-l, 71.2%

butene-Z-trans and 26.6% butene-Z-cis),

28.1% C -olefines (of which 0.8% 3-methylpenetene-1,

20.3% 2-ethylbutene-1, 9.6% hexene-Z-trans, 23.0% 3-methylpentene-Z-trans, 2.6% hexene-Z-cis and 43.7% 3-methylpentene-2-cis1.3% C -olefines and higher.

EXAMPLE 41 Temperature: 40 C.

Pressure: 1 atm.

Solvent: n-heptane, 25 ml.

Monomer: Ethene.

Catalyst, mg. NiBI'g' [P(C5H11)3]2, mg. NiBI'z [P(-n-butyl) and 63.48mg. Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 4 ml.

Composition of product 75.7% C -olefines (of which 2.6% butene-l, 68.8%

butene-Z-trans and 28.6% butene-Z-cis),

22.5% C -olefins (of which 2.6% 3-methylpentene-1, 4.3%hexene-3-cis/trans, 15.6% 2 ethylbutene 1, 12.8% hexene-Z-trans, 20.8%3-methylpentene-2-trans, 4.3% hexene-Z-cis and 39.6%3-methylpentene-2-cis),

1.8% c -olefines and higher.

19 EXAMPLE 42 Temperature: 40 C.

Pressure: 1 atm.

Solvent: 25 mL-n-heptane.

Monomer: Ethene.

Catalyst: 3.71 mg. NiBr -[(C H P(CH P(C H and 63.48 mg. Al(ethyl)ClReaction time: 30 min.

Reaction product formed: 4 ml.

Composition of product 67.6% C -olefines (of which 6.7% butene-l, 59.5%

butene-2-trans and 33.8% but'ene-Z-cis),

28.4% C -olefins (of which 10.3% 3-methylpentene-1,

0.5% hexene-1, 2.3% hexene-3-cis/trans, 35.3% 2- ethylbutene-l, 10.5%hexene-2-trans, 14.9% 3-methylpentene-Z-trans, 3.5% hexene-Z-cis and22.7% 3- methylpentene-Z-cis 4.0% C -olefins and higher.

EXAMPLE 43 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 40.8 mg. cobalt(ll)chloride- [P(pheny1) 32.7 mg. P(phenyl) and62.0 mg. Al(ethyl) Cl Reaction time: 60 min.

Reaction product formed: 6 ml.

Composition of product 99% C -olefins (of which 2.0% butene-l,

butene-2-trans and 28.6% butene-2-cis),

1% C -olefins (of which 8.5% hexene-3-ci s/trans, 25.9% Z-ethylbutene-l,26.4% hexene-Z-trans, 9.1% 3-methylpentene-Z-trans, 8.7% hexene-Z-cisand 21.4% 3- methylpentene-Z-cis EXAMPLE 44 Temperature: 40 C.

Pressure: 1 atm.

Solvent: 25 ml. n-heptane.

Monomer: EthenezPropene (1:1)

Catalyst: 3.85 mg. NiBr -[PH(C H and 63.48 mg.

Al(ethyl)Cl Reaction time: 30min.

Reaction product formed: 2 ml.

Composition of product EXAMPLE 45 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 81.7 mg. NiC1 -[P(C H 3.2 mg.

Al(ethyl)Cl and 66.7 mg. AlBr Reaction time: 15 min.

Reaction product formed: 16 ml.

Composition of product 93.5% C -olefines (of which 0.5%4-methylpentene-1,

2.2% 4-methylpentene-2-cis, 7.6% 2,3-dimethylbutene- 19.1%4-methylpentene-2-trans, 9.6% Z-methylpentene- 1, 3.6% hexene-3-cis/trans, 10.5% hexene-Z-trans, 40.9% 2-methylpentene-2, 3.6% hexene-Z-cisand 2.4% 2,3-dimethylbutene-2 6.5% C -olefines and higher.

EXAMPLE 46 Temperature: 20 C.

Pressure: 1 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Propene.

Catalyst: 22.0 mg. Ni(acetate) and 104.3 mg.

A1(0C H C1 Reaction time: 30 min.

Reaction product formed: 5 m1.

Composition of product 93% C -olefines (of which 0.4% 4-methylpentene-1,

2.2% 4-methylpentene-2-cis, 0.8% 2,3-dimethylbutene- 1, 16.9%4-methylpentene-2-trans, 5.4% Z-methylpentene-l, 4.7%heXene-3-cis/trans, 11.8% hexene-2-trans, 49.8% 2-methylpentene-2, 3.8%hexane-Z-cis and 4.2% 2,3-dimethylbutene-2) 7% c -olefines and higher.

EXAMPLE 47 Temperature: 40 C.

Pressure: 1 atm.

Solvent: 23.75 ml. chlorobenzene.

Monomer: Ethene/propene (1/1 gas volume) Catalyst: 5.04 mg.[P(cycloheXyl) -Ni(Cl-acetate) 1.25 ml. of a chlorobenzene solutioncontaining 100 mmoles/l of .P(cyclohexyl) +200 mmoles/l of A1(ethyl)C1preheated to 40 C. for one hour.

Reaction time: 30 min.

Reaction product formed: 5 m1.

Composition of product 21.2% C -olefines (of which 8.9% butene-l, 50.0%

butene-Z-trans and 41.1% butene-Z-cis),

44.6% C olefines (of which 93.0% methylbutenes and 7.0% n-pentenes),

24.2% C -olefines,

10.0% c -olefines and higher.

EXAMPLE 48 Temperature: 40 C.

Solvent: 12.5 ml. chlorohenzene.

Monomer: Butene, 12.5 mL, Propene (50 ml./min.).

Catalyst: 50.5 mg. Ni(trichloroacetate) -[P(n-butyl) and 15.87 mg.Al(ethy1) C1 Reaction time: 60 min.

Composition of product In addition to unreacted butene,

3.8 grams C -olefines, 4.0 grams C olefines and 1.1 grams C -olefinesand higher,

are obtained.

EXAMPLE 49 Temperature: 7 /2 C.

Pressure: 1 atm.

Solvent: 25 m1. chlorobenzene.

Monomer: 2.4 g. butene, 60% butane-1, 12% butene-Z- cis, 28%butene-Z-trans) Catalyst: 8.1 mg. NiCl -[P(n-buty1) and 63.48 mg.

A1(ethyl)C1 Reaction time: min.

C -olefines formed: 1.1 grams.

EXAMPLE 50 Temperature: C.

Pressure: 40 atm.

Solvent: 25 ml. benzene.

Monomer: Ethene.

Catalyst: 4.1 mg. NiCl -[P(phenyl) and 15.87 mg.

Al(ethyl)Cl Reaction time: 30 min.

Reaction product formed: 30 ml.

Composition of product 6 /2% C -olefines (of which 3.5% butene-l, 67.0%butene-Z-trans and 30.5% butene-Z-cis),

30% C -olefines (of which 0.8% 3-methylpentene-l, 16.4% 2-ethylbutene-1,15.8% hexene-Z-trans, 21.5% 3-methylpentene-2-trans, 3.8% hexene-Z-cisand 41.6% 3 -methylpentene-2- cis 10% C -olefines and higher.

EXAMPLE 51 Temperature: C.

Pressure: 4 atm.

Solvent: m1. chlorobenzene.

Monomer: Ethene.

Catalyst: 13.4 mg. NiCl -[P(n-buty1) and 15.87 mg.

A1(ethyl)Cl Reaction time: min.

Reaction product formed: 55 ml.

Composition of product 42.2% C -olefines (of which 1.7% butene-l, 66.2%bu- Iene-Z-trans and 32.1% butene-Z-cis),

53.4% C -olefines (of which 0.8% 3-methylpentene-1, 1.6%hexene-3-cis/trans, 8.9% 2-ethylbutene-1, 5.3% heXene-Z-trans, 29.4%3-methylpentene-2-trans, 1.8% hexene-2-cis and 52.2%3-methylper1tene-2-ciS),

4.4% C -olefines and higher.

EXAMPLE 52 Temperature: 20 C.

Pressure: 4 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 81.8 mg NiCl -[p(phenyl) and 133.3 mg.

AlBI's Reaction time: 30 min.

Reaction product formed: 15 ml.

Composition of product 90.1% C -olefins (of which 3.3% butene-l, 67.7%butene-Z-trans and 29.0% butene-Z-cis),

5.2% C -olefins (of which 7.2% 3-methylpentene-1, 0.6% hexene-l, 11.2%hexene-S-cis/trans and 2-ethylbutene- 1, 26.4% hexene-Z-trans, 13.3%3-methylpentene-2- trans; 8.6% hexene-Z-cis and 32.7% 3-methy1pentene-2-cis 4.7% C -olefins and higher.

EXAMPLE 5 3 Temperature: 40 C.

Pressure: 5 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 13.7 mg. NiBr 46.5 mg. diphenyl sulfide and 127 mg.A1(ethyl)Cl Reaction time: 60 min.

Reaction product formed: 7 ml.

Composition of product 50.8% C -olefines (of which 13.7% butene-l, 59.7%butene-2-trans and 26.6% butene-Z-cis),

24.9% C -o1efines (of which 4.3% 3-methylpentene-1,

3.7% hexene-l, 21.6% hexene-S-cis/trans and 2-ethyl- 22 butene-l, 44.7%hexene-2-trans, 2.9% 3-methylpentene-Z-trans, 15.2% hexene-2-cis and7.6% 3-methy1- pentene-Z-cis), 24.3% C -olefines and higher.

EXAMPLE 54 Temperature: 40 C.

Pressure: 5 atm.

Solvent: 25 ml. chlorobenzene.

Monomer: Ethene.

Catalyst: 13.7 mg. NiBr 18 mg. tetrahydrofuran and 127 mg. Al(ethy1)ClReaction time: 60 min.

Reaction product formed: 16 ml.

Composition of product 46.3% C -olefins (of which 11.1% butene-l, 62.0%bu- 1 tene-Z-trans and 26.9% butene-Z-cis),

33.0% C -olefins (of which 3.4% 3-methylpentene-1,

3.1% hexene-l, 21.2% hexene-3-cis/trans and 2-ethy1- butene-l, 43.3%heXene-2-trans, 4.2% 3-methylpentene-Z-trans, 14.5% hexene-Z-cis and10.2% 3-methy1- pentene-Z-cis),

20.7% c -olefines and higher.

What is claimed is:

1. In a process for the preparation of mono-olefines having a highcontent of fl-olefines in the range of C -C by conversion bydimerization, codimerization, polymeri zation and copolymerization ofthe mono-olefines, the improvement wherein olefines from the range C -Care converted in the presence of a catalyst system comprising:

(a) a transition metal compound selected from the group consisting ofnickel acetate, cobalt acetate, nickel chloroacetate, and nickeltrichloroacetate,

(b) a Lewis acid of the formula AlR Y wherein R is an alkyl group, Y isselected from the group consisting of halide and alcoholate groups, andb=02, and

(c) a Lewis base selected from the group consisting of alkylphosphine,cycloalkyl phosphine and phenyl phosphine at the temperature at whichthe transition metal in the transition metal compounds is notsubstantially reduced to metallic form.

2. The improvement according to claim 1, wherein the Lewis base isselected from the group consisting of tri-nbutyl-phosphine,tri-cyclohexyl-phosphine and tri-phenylphosphine.

3. The improvement according to claim 1, wherein the transition metalcompound is selected from the group consisting of nickel acetate andcobalt acetate, the Lewis acid is ethyl aluminum chloride and the Lewisbase is tri-phenylphosphine.

References Cited UNITED STATES PATENTS 252-428, 429 B, 431 C, 431 N, 431P; 260-6832

